CN110028754A - A kind of micro-ablation lightweight phenolic resin and preparation method thereof - Google Patents
A kind of micro-ablation lightweight phenolic resin and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The present invention relates to a kind of micro-ablation lightweight phenolic resin and preparation method thereof.The micro-ablation lightweight phenolic resin is made of 100 parts of phenolic resin, 5~15 parts of hollow phenolic aldehyde microballon, 3~8 parts of nano-titanium dioxide, 5~20 parts of hollow glass micropearl, 5~15 parts of zirconium diboride and 0.3~0.8 part of toughener based on parts by weight.The preparation method is that: hollow phenolic aldehyde microballon, nano-titanium dioxide, hollow glass micropearl and zirconium diboride are uniformly mixed, mixed fillers are obtained, then the mixed fillers are divided into etc. to more parts of weight；Toughener is added into phenolic resin and stirs evenly, obtains mixture；The more parts of mixed fillers are sequentially added in mixture and stirred evenly, micro-ablation lightweight phenolic resin is made.The present invention significantly improves the ablation resistance of material under the premise of reducing the density of material, and micro-ablation lightweight phenolic resin density of the present invention is small, ablation resistance is excellent.
Description
Technical field
The invention belongs to polymer modification technology field more particularly to a kind of micro-ablation lightweight phenolic resin and its preparations
Method.
Background technique
Phenols and aldehyde condensation polymer product are commonly referred to as phenolic resin.Phenolic resin is to realize industrialized production earliest in the world
Synthetic resin, have exceed century-old history so far.Phenolic resin is since it is with excellent mechanicalness, heat resistance, cold-resistant
Property, dimensional stability, molding processibility, anti-flammability and low smoke and the advantages that low production cost, be still used as resin so far
The main base resin of base ablation resistant material.It is being navigated using the high temperature resistant solar heat protection ablator that phenolic resin is manufactured as matrix resin
The national defence sophisticated technology such as empty space flight field is applied widely.
Thermal protection system (Thermal Protection System, TPS) is that protection spacecraft smoothly returns to the earth
Key structure, wherein ablative thermal protection is most reliable solar heat protection scheme.Charring type ablator is suitable for high enthalpy, high heat flux density
Service Environment, be the thermal-protect ablation material being widely used at present, Typical Representative is carbon/phenolic aldehyde (C-Ph) composite material.It passes
C-Ph polymer matrix composites density of uniting is larger and thermal coefficient is higher, is difficult to meet high-performance aerospace field, loss of weight
It is the eternal pursuit of aerospace, therefore heat-resistant light ablative-insulative material is the hot spot of research in recent years.
In, low-density composite have good heat-proof quality, be another after high silicone/phenolic resin composite material
It is that the resistance to ablation of a new generation strongly developed of the U.S., carrying, the heat-insulated a new generation's heat being integrated are anti-for novel thermal-protect ablation material
Protective material.On many deep space exploration aircrafts, a large amount of low-density composites will be used, and explore the moon, Mars,
One of recoverable spacecrafts thermal protection system preferred material such as Jupiter, Saturn, Neptune.
Can ceramic fluidized polymer it is very concerned in high temperature flame-proof fire resisting field, can ceramic fluidized polymer in low temperature environment
With the performance similar with general polymer, and under high temperature environment, secondary chemical reaction itself will occur and be converted to pottery
Porcelain.The ceramic product of generation has better heatproof, impact resistance ability than before, to guarantee that internal product is not encroached on.It can
The high Hygrothermal Aging high molecular material of the resistance to limit of ceramic rely primarily on addition it is therein realize fast ceramic at porcelain filling,
This mainly includes reactive inorganic filler (or its presoma) and/or low softening point fluxing agent (or its forerunner at porcelain filling
Body).Chinese patent application CN201810372140.X discloses a kind of anti-heat-insulation integrative resin combination, prevents heat-insulated one
Change resin base ablator and preparation method thereof, the composition is filled out comprising 100 parts of phenolic resin, ceramics based on parts by weight
10~20 parts of material, 5~15 parts of tiny balloon and appropriate modifier, the patent application are same in the phenolic resin comprising modifying agent
When be added to ceramic packing with anti-ablation effect and with the tiny balloon for reducing heat transfer effect, obtained the anti-thermal energy of collection
The anti-heat-insulation integrative resin combination of power and heat-insulating capability one, but use the anti-heat-insulation integrative of the composition preparation
Resin base ablator also can only achieve 72.9% in 600 DEG C of Residual carbon highest, and ablation resistance is poor, and this it is anti-every
The density of heating integrated resin base ablator is larger.
In view of the above problems, a kind of micro-ablation lightweight phenol that be highly desirable to provide low-density, that ablation resistance is excellent
Urea formaldehyde and preparation method thereof.
Summary of the invention
It is existing to solve the purpose of the invention is to provide a kind of micro-ablation lightweight phenolic resin and preparation method thereof
Technical problem present in technology.The present invention significantly improves the ablation resistance of material under the premise of reducing the density of material
Can, micro-ablation lightweight phenolic resin of the present invention has the advantages that density is small, ablation resistance is excellent.
To achieve the goals above, the present invention provides a kind of micro-ablation lightweight phenolic resin in first aspect, described micro-
Ablation lightweight phenolic resin is by 100 parts of phenolic resin, 5~15 parts of hollow phenolic aldehyde microballon, nanometer titanium dioxide based on parts by weight
3~8 parts of titanium, 5~20 parts of hollow glass micropearl, 5~15 parts of zirconium diboride and 0.3~0.8 part of toughener composition.
Preferably, the micro-ablation lightweight phenolic resin is by 100 parts of phenolic resin, hollow phenolic aldehyde based on parts by weight
5~15 parts of microballon, 5 parts of nano-titanium dioxide, 5~20 parts of hollow glass micropearl, 5~15 parts of zirconium diboride and 0.5 part of toughener
Composition.
Preferably, the micro-ablation lightweight phenolic resin is by 100 parts of phenolic resin, hollow phenolic aldehyde based on parts by weight
10~15 parts of microballon, 5 parts of nano-titanium dioxide, 10~20 parts of hollow glass micropearl, 5~15 parts of zirconium diboride and toughener 0.5
Part composition.
Preferably, the phenolic resin is ba phenolic resin.
Preferably, the partial size of the hollow phenolic aldehyde microballon is 5~300um, and density is 0.1~0.25g/cm3。
Preferably, the density of the nano-titanium dioxide is 3.8~3.9g/cm3。
Preferably, the melting temperature of the hollow glass micropearl is 400~600 DEG C.
Preferably, the density of the micro-ablation lightweight phenolic resin is less than 1.1g/cm3, Residual carbon at 900 DEG C is greater than
70%.
The present invention provides the preparation of micro-ablation lightweight phenolic resin of the present invention described in first aspect in second aspect
Method, described method includes following steps:
(1) by 5~15 parts of hollow phenolic aldehyde microballon, 3~8 parts of nano-titanium dioxide, 5~20 parts of hollow glass micropearl and two
5~15 parts of zirconium boride are uniformly mixed, and obtain mixed fillers, then the mixed fillers are divided into etc. to more parts of weight；
(2) 0.3~0.8 part of toughener is added into 100 parts of phenolic resin and stirs evenly, obtains mixture；
(3) the more parts of mixed fillers for obtaining step (1) are sequentially added in the mixture that step (2) obtains and are stirred
It mixes uniformly, micro-ablation lightweight phenolic resin is made.
Preferably, in step (2), the phenolic resin is the phenolic aldehyde tree for carrying out the pre-heat treatment at 60~70 DEG C and crossing
Rouge；And/or in step (2), the time of the stirring is 15~20min；And/or in step (3), a institute of every addition
When stating mixed fillers into the mixture, the time of stirring is 10~20min.
The present invention at least have compared with prior art it is following the utility model has the advantages that
(1) the Nano titanium dioxide fusing point that the micro-ablation lightweight phenolic resin in the present invention contains is high, is conducive to
The heat resistance and Residual carbon for improving resin, improve the ablation resistance of resin.
(2) hollow phenolic aldehyde microballon and hollow glass micropearl that the micro-ablation lightweight phenolic resin in the present invention contains
As the functional stuffing of resistance to ablation, the advantages of density of material is effectively reduced in the two has been played；Importantly, hollow glass micropearl
The addition that especially low melting point hollow glass micropearl is added crack temperature in phenolic resin main chain because it is with lower fusing point
It spends in range, the glass microballoon of addition, which melts, internally flows into (infiltration), hinders the entrance of oxygen, reduces the oxygen of resin matrix
Change and decomposes, so that the ablation resistance of resin is improved, and the addition of the hollow phenolic aldehyde microballon increases remaining filler and phenol
The touch opportunity of urea formaldehyde improves the fusion rate of filler and phenolic resin, keeps filler not easy to reunite, is conducive to obtain density
Uniformly, the stable micro-ablation lightweight phenolic resin of ablation resistance.
(3) zirconium diboride that the micro-ablation lightweight phenolic resin in the present invention contains is ceramic forerunner, it adds
Enter and increase ceramic layer during material ablation, improve the anti-shear ability of material and hinder the entrance of oxygen, mentions
High ablation resistance.
(4) in the present invention, the addition of low-melting glass microballon, zirconium diboride and nano-titanium dioxide makes the resistance to of material
Ablation temperature gradient distribution increases, and adapts to the hot-fluid environment of different temperatures.
(5) present invention significantly improves the ablation resistance of material, institute of the present invention under the premise of reducing the density of material
The micro-ablation lightweight phenolic resin stated has the advantages that density is small, ablation resistance is excellent, and density is less than < 1.1g/cm3,
Residual carbon > 70% at 900 DEG C.
(6) mixed fillers are divided into more parts and sequentially added in the mixture comprising phenolic resin by the method for the present invention,
Advantageously ensure that the stable micro-ablation lightweight phenolic resin of obtained even density, ablation resistance.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this
The technical solution of invention is clearly and completely described, it is clear that and described embodiment is a part of the embodiments of the present invention,
Instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative labor
Every other embodiment obtained under the premise of dynamic, shall fall within the protection scope of the present invention.
The present invention provides a kind of micro-ablation lightweight phenolic resin, the micro-ablation lightweight phenolic resin in first aspect
By based on parts by weight 100 parts of phenolic resin, 5~15 parts of hollow phenolic aldehyde microballon (such as 5,6,7,8,9,10,11,12,13,
14 or 15 parts), 3~8 parts of nano-titanium dioxide (such as 3,4,5,6,7 or 8 parts), 5~20 parts of hollow glass micropearl (such as 5,
6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 parts), 5~15 parts of zirconium diboride (such as 5,6,7,8,9,
10,11,12,13,14 or 15 parts) and 0.3~0.8 part of toughener (such as 0.3,0.4,0.5,0.6,0.7 or 0.8 part) group
At.In the present invention, the hollow phenolic aldehyde microballon and the hollow glass for including in the micro-ablation lightweight phenolic resin are micro-
The total weight percentage composition of pearl is no more than 35%；In the present invention, the toughener for example can be carboxy nitrile rubber
The composition of (such as nbr carboxyl terminal) or polyvinyl butyral or carboxy nitrile rubber and polyvinyl butyral；
In the present invention, different from the modifying agent of compatibility of two or more components is improved, the toughener is added to
Improve mixture after filler (hollow phenolic aldehyde microballon, nano-titanium dioxide, hollow glass micropearl, zirconium diboride filler) is added
Film forming, the viscosity of matrix can be reduced by being added after filler with to solve general resin, so that matrix hair " dry ", cannot be made into preimpregnation
The problem of material, filming performance reduces.
In the present invention, the nano-titanium dioxide fusing point is high, heat-resist, be conducive to the heat resistance for improving resin and
Residual carbon improves the ablation resistance of resin；The hollow phenolic aldehyde microballon and the hollow glass micropearl are as the function of resistance to ablation
Energy filler, has played the advantages of resin matrix density is effectively reduced in the two；Importantly, low melting point hollow glass micropearl exists
On ablative mechanism, because it is with lower fusing point, in phenolic resin main chain crack temperature range, the glass microballoon of addition melts
Change and internally flow into (infiltration), hinders the entrance of oxygen, reduce the oxygenolysis of resin matrix, to improve the resistance to of resin
Ablation property, and the addition of the hollow phenolic aldehyde microballon increases the touch opportunity of remaining filler and phenolic resin, improves and fills out
The fusion rate of material and phenolic resin, keeps filler not easy to reunite, is conducive to obtain the stable micro- burning of even density, ablation resistance
Lose lightweight phenolic resin；In the present invention, the addition of the zirconium diboride increases ceramic layer during material ablation, mentions
The high anti-shear ability of material and the entrance of oxygen is hindered, improves ablation resistance；In the present invention, hollow phenol
The addition of aldehyde microballon, hollow glass micropearl is so that the density of material reduces, and low-melting glass microballon, zirconium diboride and nanometer
The addition of titanium dioxide increases the gradient distribution of resistance to ablation temperature of material, adapts to the hot-fluid environment of different temperatures, in the present invention
The hollow phenolic aldehyde microballon, hollow glass micropearl, zirconium diboride and nano-titanium dioxide play modified synergic phenolic resin
Effect.In the present invention, the addition of low-melting glass microballon, zirconium diboride and nano-titanium dioxide enables to micro- burning
The gradient distribution of resistance to ablation temperature for losing lightweight phenolic resin increases mainly since the main chain cracking temperature of phenolic resin is at 350 DEG C
~400 DEG C, carbonization is at 800 DEG C or so, if flight vehicle aerodynamic heat only has 500 DEG C or so, and its carbonization time cannot replace
Temperature influences carbonisation, therefore prolonged low temperature aerobic environment will increase ablation amount, reduce ablation protection performance, eutectic
The addition of point hollow glass micropearl can gradually melt trickling after temperature is greater than 400 DEG C, fill up ablation hole, block oxygen
Into low temperature ablative protective performance in raising；And under high temperature environment (1000 DEG C or so), the phenolic resin after carbonization can rise
China is removed by air-flow, and the addition of nano-titanium dioxide, zirconium diboride filler can generate ceramic layer under high temperature environment, is continued
Starvation and airflow scouring improve high temperature ablation protective performance, so that the gradient distribution of resistance to ablation temperature of material increases.
The inventors discovered that in the present invention, the hollow phenolic aldehyde microballon, the nano-titanium dioxide, the hollow glass
The missing of any component in glass microballon, the zirconium diboride and the toughener not can guarantee to obtain density low, resistance to
The excellent micro-ablation lightweight phenolic resin of ablation property, that is, not can guarantee hollow phenolic aldehyde microballon, hollow glass micropearl and two
The effect of the modified synergics such as zirconium boride；Also, the inventors discovered that hollow this component of phenolic aldehyde microballon can function well as raising
The effect that the fusion rate of filler and phenolic resin keeps filler not easy to reunite, to be conducive to obtain even density, ablation resistance
Stable micro-ablation lightweight phenolic resin, and other cenospheres (such as hollow glass micropearl (glass hollow microballoon) or dioxy
SiClx cenosphere (SiO 2 hollow microsphere)) it can not substitute the hollow phenolic aldehyde microballon and play and improve filler and phenolic aldehyde
The effect of the fusion rate of resin；In addition, the inventors discovered that, in micro-ablation lightweight phenolic resin system of the present invention,
Zirconium diboride can cooperate well with low-melting glass microballon and nano-titanium dioxide, make the high temperature ablation resistance of material
Dramatically increase, and other ceramic packings other such as zirconium oxide, boron oxide then with hollow glass micropearl, nano-titanium dioxide
Deng fiting effect it is bad.
According to some preferred embodiments, the micro-ablation lightweight phenolic resin is by phenolic aldehyde tree based on parts by weight
100 parts of rouge, 5~15 parts of hollow phenolic aldehyde microballon (such as 5,6,7,8,9,10,11,12,13,14 or 15 parts), nano-titanium dioxide 5
Part, 5~20 parts of hollow glass micropearl (such as 5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 parts),
5~15 parts of zirconium diboride (such as 5,6,7,8,9,10,11,12,13,14 or 15 parts) and 0.5 part of toughener composition.Many institute's weeks
Know, Residual carbon is an important indicator for measuring phenolic resin ablative energy, and the higher phenolic resin ablation resistance of Residual carbon is more
It is good, and the Residual carbon of phenolic resin is related with ablation temperature, phenolic resin is easier to keep under lower ablation temperature
Higher Residual carbon, and under such as 800~1000 DEG C of high temperature ablation (high ablation temperature), phenolic resin can be due to fast
Fast ablation and cause Residual carbon to reduce, it is residual and it is well known that ablation resistance of the phenolic resin under high temperature ablation is poor
Carbon rate is difficult to be promoted to 70% and be just more difficult to realize promotion on the basis of Residual carbon is 70%；The present invention is by using suitable
Hollow phenolic aldehyde microballon, nano-titanium dioxide, hollow glass micropearl, zirconium diboride and the toughener of proportion are to the phenolic resin
It is modified, so that micro-ablation lightweight phenolic resin system of the present invention significantly mentions under the premise of reducing density of material
High the ablation resistance of material (Residual carbon is high), so that the density of the micro-ablation lightweight phenolic resin can be with < 1.1g/
cm3, Residual carbon > 70% at 900 DEG C.In addition, the inventors discovered that, in the case where its Ingredient Amount is constant, preferably
The dosage of the nano-titanium dioxide is 5 parts by weight, and the dosage of the preferably described toughener is 0.5 parts by weight, such energy
It is further ensured that the density < 1.1g/cm of the micro-ablation lightweight phenolic resin3, Residual carbon > 70% at 900 DEG C.
According to some preferred embodiments, the micro-ablation lightweight phenolic resin is by phenolic aldehyde tree based on parts by weight
It is 100 parts of rouge, 10~15 parts of hollow phenolic aldehyde microballon (such as 10,11,12,13,14 or 15 parts), 5 parts of nano-titanium dioxide, hollow
10~20 parts of glass microballoon (such as 10,11,12,13,14,15,16,17,18,19 or 20 parts), 5~15 parts of zirconium diboride and
0.5 part of toughener composition.In the present invention, in the case where its Ingredient Amount is constant, the preferably described hollow phenolic aldehyde microballon is
10~15 parts, the hollow glass micropearl be 10~20 parts, can so guarantee the density of the micro-ablation lightweight phenolic resin
< 0.95g/cm3, Residual carbon > 74% at 900 DEG C, can significantly reduce the density of the micro-ablation lightweight phenolic resin with
And further increase ablation resistance.
According to some preferred embodiments, the phenolic resin is ba phenolic resin.In the present invention, the barium phenol
Urea formaldehyde for example can be the solvent-free phenolic aldehyde of 251 factories, the product main chain cracking temperature after solidification at 350 DEG C~400 DEG C or so,
Residual carbon at 900 DEG C is 62%.
According to some preferred embodiments, the partial size of the hollow phenolic aldehyde microballon is 5~300um, density is 0.1~
0.25g/cm3。
According to some preferred embodiments, the density of the nano-titanium dioxide is 3.8~3.9g/cm3；In this hair
In bright, the density of the preferably described nano-titanium dioxide is 3.8~3.9g/cm3, because its fusing point is at 1800 DEG C or so, heat resistance
It is good, be conducive to the heat resistance and Residual carbon that improve resin.
According to some preferred embodiments, the melting temperature of the hollow glass micropearl is 400~600 DEG C.In this hair
In bright, the low melting point hollow glass micropearl that melting temperature is 400~600 DEG C has lower fusing point, splits in phenolic resin main chain
It solves in temperature range, the glass microballoon of addition, which melts, internally flows into (infiltration), hinders the entrance of oxygen, reduces resin matrix
Oxygenolysis, be conducive to improve resin matrix ablation resistance.
According to some preferred embodiments, the density of the micro-ablation lightweight phenolic resin is less than 1.1g/cm3, 900
DEG C when Residual carbon be greater than 70%.
According to some preferred embodiments, the density of the micro-ablation lightweight phenolic resin is less than 0.95g/cm3, 900
DEG C when Residual carbon be greater than 74%.
The present invention provides the preparation of micro-ablation lightweight phenolic resin of the present invention described in first aspect in second aspect
Method, described method includes following steps:
(1) by 5~15 parts of hollow phenolic aldehyde microballon, 3~8 parts of nano-titanium dioxide, 5~20 parts of hollow glass micropearl and two
5~15 parts of zirconium boride are uniformly mixed, and obtain mixed fillers, then the mixed fillers are divided into etc. to more parts (two parts of weight
And two parts or more)；
(2) 0.3~0.8 part of toughener is added into 100 parts of phenolic resin and stirs evenly, obtains mixture；
(3) the more parts of mixed fillers for obtaining step (1) are sequentially added in the mixture that step (2) obtains and are stirred
It mixes uniformly, micro-ablation lightweight phenolic resin is made.
It illustrates, " part " in the present invention refers to parts by weight.
The mixed fillers are divided into more parts and are sequentially added in the mixture comprising phenolic resin by the present invention using this
Mode, it is ensured that the mixed fillers mix more uniform with the mixture, advantageously ensure that obtained density is equal
The micro-ablation lightweight phenolic resin even, ablation resistance is stable.
According to some preferred embodiments, in step (1), the mixed fillers are divided into etc. three parts of weight.
In the present invention, for the mixed fillers are divided into 3 parts, such as this 3 parts of mixed fillers can be successively denoted as first
Part mixed fillers, second part of mixed fillers and third mixed fillers, i.e., the described mixed fillers are by first part of mixed fillers, second
Part mixed fillers and third part mixed fillers composition.
According to some preferred embodiments, in step (2), the phenolic resin is to carry out in advance at 60~70 DEG C
Heat treated phenolic resin；And/or in step (2), the time of the stirring is 15~20min；And/or in step (3)
In, when a mixed fillers of every addition are into the mixture, it is preferably 15min that the time of stirring, which is 10~20min,.
According to some specific embodiments, the micro-ablation lightweight phenolic resin includes the following steps:
The pretreatment of S1, phenolic resin:
Phenolic resin as matrix resin strand is larger, is solid under normal temperature state, 100 parts of phenolic resin are put into baking oven
Middle preheating 5h or so, oven temperature is advisable at 60 DEG C~70 DEG C (preheating temperature).
S2, filler pre-treatment:
First in a reservoir by each accounting each component filler investment, premixing 0.5h is stirred using agitating paddle, to guarantee to stir
Uniformly, mixed fillers are obtained, is more advantageous to and subsequent is mixed with the mixture comprising the phenolic resin；Each component parts by weight
Are as follows: 5~15 parts of hollow phenolic aldehyde microballon, 5 parts of nano-titanium dioxide, 5~20 parts of hollow glass micropearl, 5~15 parts of zirconium diboride,
Hollow phenolic aldehyde microballon and the total accounting of hollow glass micropearl just can guarantee technological feasibility, if more than 35% no more than 35%
It is subsequent bad with the Combination of mixture to will lead to mixed fillers, to not can guarantee the feasibility of technique.
S3, reaction kettle is preheated to 60 DEG C, turns off heating.The phenolic resin that the pre-heat treatment is crossed pours into described anti-
It answers in kettle, then 0.5 part of toughener is uniformly sprinkled into the reaction kettle, stir 15min~20min, obtain mixture.
S4, part that the mixed fillers in S2 classify in three categories sequentially add in the mixture, every primary stirring of addition
15min, until finally all mixed fillers are all added, resin combination, which stirs evenly, can be obtained micro-ablation lightweight phenol
Urea formaldehyde.
Hereafter the present invention will be further detailed by way of example, but protection scope of the present invention is not
It is limited to these embodiments.
Embodiment 1
1. weighing hollow phenolic aldehyde microballon 50g, nano-titanium dioxide 50g, hollow glass micropearl 50g, zirconium diboride 50g to throw
Enter in container, stirs premixing 0.5h using agitating paddle, obtain mixed fillers, the mixed fillers such as are then divided at the weight
3 parts of amount are stand-by；Wherein, hollow glass micropearl is selected from the low melting point hollow glass micropearl that melting temperature is 400~600 DEG C.
2. weighing in the reaction kettle after the ba phenolic resin after the pre-heat treatment of 1kg pours into preheating, 5g toughening is then added
20min is sufficiently stirred in agent, to be dissolved completely in the ba phenolic resin matrix, obtains mixture.
3. sequentially added in 2. mixture that step obtains step 1. in be divided into 3 parts of mixed fillers, often plus
Enter primary stirring 15min, until finally all mixed fillers are all added, resin combination stir evenly can be obtained it is micro-
Ablation lightweight phenolic resin.
By the micro-ablation lightweight phenolic resin in the present embodiment after molded curing, analysis measures density 1.02g/
cm3, the Residual carbons of 500 DEG C of heat preservation 10min are 91.8%, and the Residual carbon (900 DEG C of Residual carbons) at 900 DEG C is 71.2%；?
In the present invention, 900 DEG C of Residual carbon is referred to through thermogravimetric analyzer, under the test environment of oxygen atmosphere, with 10 DEG C/
The heating rate of min is warming up to the Residual carbon of the material measured at 900 DEG C.
Embodiment 2
1. weighing hollow phenolic aldehyde microballon 100g, nano-titanium dioxide 50g, hollow glass micropearl 100g, zirconium diboride 100g
It puts into container, stirs premixing 0.5h using agitating paddle, obtain mixed fillers, be then divided into the mixed fillers
3 parts of weight are stand-by；Wherein, hollow glass micropearl is selected from the low melting point hollow glass micropearl that melting temperature is 400~600 DEG C.
2. weighing in the reaction kettle after the ba phenolic resin after the pre-heat treatment of 1kg pours into preheating, 5g toughening is then added
20min is sufficiently stirred in agent, to be dissolved completely in the ba phenolic resin matrix, obtains mixture.
3. sequentially added in 2. mixture that step obtains step 1. in be divided into 3 parts of mixed fillers, often plus
Enter primary stirring 15min, until finally all mixed fillers are all added, resin combination stir evenly can be obtained it is micro-
Ablation lightweight phenolic resin.
By the micro-ablation lightweight phenolic resin in the present embodiment after molded curing, analysis measures density 0.93g/
cm3, Residual carbon at 900 DEG C is 74.7%.
Embodiment 3
1. weighing hollow phenolic aldehyde microballon 150g, nano-titanium dioxide 50g, hollow glass micropearl 150g, zirconium diboride 150g
It puts into container, stirs premixing 0.5h using agitating paddle, obtain mixed fillers, be then divided into the mixed fillers
3 parts of weight are stand-by；Wherein, hollow glass micropearl is selected from the low melting point hollow glass micropearl that melting temperature is 400~600 DEG C.
2. weighing in the reaction kettle after the ba phenolic resin after the pre-heat treatment of 1kg pours into preheating, 5g toughening is then added
20min is sufficiently stirred in agent, to be dissolved completely in the ba phenolic resin matrix, obtains mixture.
3. sequentially added in 2. mixture that step obtains step 1. in be divided into 3 parts of mixed fillers, often plus
Enter primary stirring 15min, until finally all mixed fillers are all added, resin combination stir evenly can be obtained it is micro-
Ablation lightweight phenolic resin.
By the micro-ablation lightweight phenolic resin in the present embodiment after molded curing, analysis measures density 0.87g/
cm3, 900 DEG C of Residual carbon is 77.3%.
Embodiment 4
1. weighing hollow phenolic aldehyde microballon 150g, nano-titanium dioxide 50g, hollow glass micropearl 200g, zirconium diboride 150g
It puts into container, stirs premixing 0.5h using agitating paddle, obtain mixed fillers, be then divided into the mixed fillers
3 parts of weight are stand-by；Wherein, hollow glass micropearl is selected from the low melting point hollow glass micropearl that melting temperature is 400~600 DEG C.
2. weighing in the reaction kettle after the ba phenolic resin after the pre-heat treatment of 1kg pours into preheating, 5g toughening is then added
20min is sufficiently stirred in agent, to be dissolved completely in the ba phenolic resin matrix, obtains mixture.
3. sequentially added in 2. mixture that step obtains step 1. in be divided into 3 parts of mixed fillers, often plus
Enter primary stirring 15min, until finally all mixed fillers are all added, resin combination stir evenly can be obtained it is micro-
Ablation lightweight phenolic resin.
By the micro-ablation lightweight phenolic resin in the present embodiment after molded curing, analysis measures density 0.72g/
cm3, 900 DEG C of Residual carbon is 77.6%.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 1, the difference is that:
In 1., the dosage of nano-titanium dioxide is 30g；In 2., the dosage of toughener is 3g.
By micro-ablation lightweight phenolic resin made from the present embodiment after molded curing, analysis measures density 1.04g/
cm3, 900 DEG C of Residual carbon is 68.5%.
Embodiment 6
Embodiment 6 is substantially the same manner as Example 4, the difference is that:
In 1., the dosage of nano-titanium dioxide is 80g；In 2., the dosage of toughener is 8g.
By micro-ablation lightweight phenolic resin made from the present embodiment after molded curing, analysis measures density 1.06g/
cm3, 900 DEG C of Residual carbon is 69.3%.
Comparative example 1
It is added to and can heat in reaction kettle 1. weighing 20kg phenolic resin, and be added to described heat in reaction kettle
300g polyvinyl alcohol modification agent, polyvinyl alcohol addition are the 1.5% of the phenolic resin gross mass, and mixed system is heated up
It to 60 DEG C, is quickly stirred 5 minutes or so with double-planet power mixer and is completely dissolved dispersion to polyvinyl alcohol, obtained comprising phenol
The mixture of urea formaldehyde and modifying agent.
2. weighing 3kg zirconium boride and 1.6kg tiny balloon in proportion, it is added in the mixture 1. obtained, and in three rollers
10min is mixed in machine, obtains mixture.
3. the mixture 2. obtained is added again to be heated in reaction kettle, with double-planet power mixer at 50 DEG C
It stirs evenly, obtains anti-heat-insulation integrative resin combination.
Anti- heat-insulation integrative resin combination prepared by this comparative example is prepared high silicone/phenolic resin by hot melt to presoak
Material；Solidified after the prepreg is cut by mould pressing process, obtains the test sample of anti-heat-insulation integrative resin base ablator
Plate tests the density 1.21g/cm of obtained anti-heat-insulation integrative resin base ablator using test piece analysis3,
900 DEG C of Residual carbon is 65.2%.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 4, the difference is that:
2. weighing in the reaction kettle after the ba phenolic resin after the pre-heat treatment of 1kg pours into preheating, the poly- second of 5g is then added
Enol modifying agent, is sufficiently stirred 20min, to be dissolved completely in the ba phenolic resin matrix, obtains mixture.
By phenol-formaldehyde resin modified made from this comparative example after molded curing, analysis measures density 1.18g/cm3, 900 DEG C
Residual carbon be 64.6%.
Comparative example 3
Comparative example 3 is substantially the same manner as Example 1, the difference is that:
1. nano-titanium dioxide 50g, hollow glass micropearl 100g are weighed, in zirconium diboride 50g investment container, using stirring
Mix paddle agitation premixing 0.5h, obtain mixed fillers, then by the mixed fillers be divided into etc. 3 parts of weight it is stand-by.
By phenol-formaldehyde resin modified made from this comparative example after molded curing, analysis measures density 1.17g/cm3, 900 DEG C
Residual carbon be 65.1%.
Comparative example 4
Comparative example 4 is substantially the same manner as Example 1, the difference is that:
1. weighing silicon dioxide hollow microballon 50g, nano-titanium dioxide 50g, hollow glass micropearl 50g, zirconium diboride
50g is put into container, is stirred premixing 0.5h using agitating paddle, is obtained mixed fillers, be then divided into the mixed fillers
Etc. 3 parts of weight it is stand-by.
By phenol-formaldehyde resin modified made from this comparative example after molded curing, analysis measures density 1.15g/cm3, 900 DEG C
Residual carbon be 64.9%.
Comparative example 5
Comparative example 5 is substantially the same manner as Example 1, the difference is that:
1. hollow glass micropearl 100g, nano-titanium dioxide 50g are weighed, in zirconium diboride 50g investment container, using stirring
Mix paddle agitation premixing 0.5h, obtain mixed fillers, then by the mixed fillers be divided into etc. 3 parts of weight it is stand-by.
By phenol-formaldehyde resin modified made from this comparative example after molded curing, analysis measures density 1.16g/cm3, 900 DEG C
Residual carbon be 64.7%.
Comparative example 6
Comparative example 6 is substantially the same manner as Example 1, the difference is that:
1. weighing hollow phenolic aldehyde microballon 50g, hollow glass micropearl 50g, zirconium diboride 50g to put into container, stirring is utilized
Paddle agitation premixing 0.5h, obtains mixed fillers, then by the mixed fillers be divided into etc. 3 parts of weight it is stand-by.
By phenol-formaldehyde resin modified made from this comparative example after molded curing, analysis measures density 1.15g/cm3, 900 DEG C
Residual carbon be 66.7%.
Comparative example 7
Comparative example 7 is substantially the same manner as Example 1, the difference is that:
1. weighing hollow phenolic aldehyde microballon 50g, nano-titanium dioxide 50g, hollow glass micropearl 50g to put into container, utilize
Agitating paddle agitation premixing 0.5h, obtains mixed fillers, then by the mixed fillers be divided into etc. 3 parts of weight it is stand-by.
By phenol-formaldehyde resin modified made from this comparative example after molded curing, analysis measures density 1.13g/cm3, 900 DEG C
Residual carbon be 64.1%.
Comparative example 8
Comparative example 8 is substantially the same manner as Example 1, the difference is that:
1. weighing hollow phenolic aldehyde microballon 50g, nano-titanium dioxide 50g, hollow glass micropearl 50g, zirconium oxide 50g investment
In container, premixing 0.5h is stirred using agitating paddle, mixed fillers is obtained, the mixed fillers such as is then divided at the weight
3 parts it is stand-by.
By phenol-formaldehyde resin modified made from this comparative example after molded curing, analysis measures density 1.12/cm3, 900 DEG C
Residual carbon be 66.2%.
Comparative example 9
Comparative example 9 is substantially the same manner as Example 1, the difference is that:
1. weighing hollow phenolic aldehyde microballon 50g, nano-titanium dioxide 50g, hollow glass micropearl 50g, boron oxide 50g investment
In container, premixing 0.5h is stirred using agitating paddle, mixed fillers is obtained, the mixed fillers such as is then divided at the weight
3 parts it is stand-by.
By phenol-formaldehyde resin modified made from this comparative example after molded curing, analysis measures density 1.12g/cm3, 900 DEG C
Residual carbon be 67.4%.
Comparative example 10
Comparative example 10 is substantially the same manner as Example 1, the difference is that:
Step 1. in it is not necessary that the mixed fillers are divided into etc. 3 parts of weight, step 3. in directly will be all
The mixed fillers are once added in 2. mixture that step obtains and stir, obtain phenol-formaldehyde resin modified.
By phenol-formaldehyde resin modified made from this comparative example after molded curing, analysis measures density 1.08g/cm3, 900 DEG C
Residual carbon be 69.6%.
Comparative example 11
Comparative example 11 is substantially the same manner as Example 1, the difference is that:
The low melting point hollow glass micropearl that melting temperature is 400~600 DEG C will be selected from and be substituted for and be selected from melting temperature
650~800 DEG C of plain hollow glass microballoon, remaining is constant.
By phenol-formaldehyde resin modified made from this comparative example after molded curing, it is 1.03g/cm that analysis, which measures density,3, 500
DEG C heat preservation 10min Residual carbon be 82.7%.
In the present invention, by micro-ablation lightweight phenolic resin made from embodiment 1, embodiment 4 and comparative example 3, comparison
Phenol-formaldehyde resin modified made from example 4, comparative example 10 after molded curing, obtains 5 test samples, measures each test respectively
The overall thickness of sample, and test sample is divided into 5 layers along its thickness direction according to the overall thickness of test sample, test every layer
The density of test sample, 900 DEG C of Residual carbon obtain this 5 layers averag density, average Residual carbon (900 DEG C), thickness direction
Density range and the Residual carbon (900 DEG C) of thickness direction the results are shown in Table 2 for range.
Table 1: the performance test results of Examples 1 to 6 and comparative example 1~10.
Table 2: embodiment 1, embodiment 4 and comparative example 3, comparative example 4, comparative example 10 thickness direction performance indicator.
The Comparative result of embodiment 1, comparative example 1, comparative example 8 and comparative example 9 is it is found that work as identical additive amount from table 1
When, the ablation resistance containing zirconium oxide (or boron oxide) component is not so good as one pack system zirconium diboride；Although this is because oxidation
The presence of zirconium particle can theoretically improve the resin cracking anti-airflow scouring ability of glass-like carbon, slow down matrix mechanical stripping, but single
The zirconia particles of component can not form " netted " pantostrat in ablated surface, be stripped simultaneously with the matrix of surrounding, because
And it cannot effectively slow down degrading for matrix；Although boron oxide fusing and vaporization absorption surface portion heat, its is volatile, burns
It is more to lose surface matrix pore quantity, the anti-airflow scouring reduced capability of material, thus one pack system boron oxide improvement is unknown
It is aobvious.It is in the present invention, equally unhelpful to improvement if being added zirconium oxide, boron oxide and zirconium boride three's mixture simultaneously,
And if increase filler dosage, will increase the density of material.
In the present invention, from the Comparative result of embodiment 1 and comparative example 11 it is found that melting temperature is 650~800 DEG C
The Residual carbon that plain hollow glass microballoon keeps the temperature 10min at 500 DEG C is rapidly reduced to 82.7%, and melting temperature be 400~
The Residual carbon of 500 DEG C of low melting point hollow glass micropearl of 600 DEG C heat preservation 10min can up to 91.8%, this is primarily due to melt
Temperature is 400~600 DEG C of low melting point hollow glass micropearl in phenolic resin main chain crack temperature range, can melt to
(infiltration) is flowed into inside phenolic resin, the entrance of oxygen is hindered, reduces the oxygenolysis of resin matrix, so as to effectively mention
The ablation resistance of high resin matrix；And the plain hollow glass microballoon of the higher melt then resistance to ablation to resin matrix is improved
Performance is substantially unhelpful, and the simple glass microballon of higher melt can not improve the middle low temperature ablative protective performance of resin matrix, can lead
Cause resin matrix ablation under middle low temperature serious.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, those skilled in the art should understand that: it is still
It is possible to modify the technical solutions described in the foregoing embodiments, or part of technical characteristic is equally replaced
It changes；And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution
Spirit and scope.
Claims (10)
1. a kind of micro-ablation lightweight phenolic resin, it is characterised in that:
The micro-ablation lightweight phenolic resin by based on parts by weight 100 parts of phenolic resin, 5~15 parts of hollow phenolic aldehyde microballon,
3~8 parts of nano-titanium dioxide, 5~20 parts of hollow glass micropearl, 5~15 parts of zirconium diboride and 0.3~0.8 part of toughener composition.
2. micro-ablation lightweight phenolic resin according to claim 1, it is characterised in that:
The micro-ablation lightweight phenolic resin by based on parts by weight 100 parts of phenolic resin, 5~15 parts of hollow phenolic aldehyde microballon,
5 parts of nano-titanium dioxide, 5~20 parts of hollow glass micropearl, 5~15 parts of zirconium diboride and 0.5 part of toughener composition.
3. micro-ablation lightweight phenolic resin according to claim 2, it is characterised in that:
The micro-ablation lightweight phenolic resin by based on parts by weight 100 parts of phenolic resin, 10~15 parts of hollow phenolic aldehyde microballon,
5 parts of nano-titanium dioxide, 10~20 parts of hollow glass micropearl, 5~15 parts of zirconium diboride and 0.5 part of toughener composition.
4. micro-ablation lightweight phenolic resin according to claim 1, it is characterised in that:
The phenolic resin is ba phenolic resin.
5. micro-ablation lightweight phenolic resin according to claim 1, it is characterised in that:
The partial size of the hollow phenolic aldehyde microballon is 5~300um, and density is 0.1~0.25g/cm3。
6. micro-ablation lightweight phenolic resin according to claim 1, it is characterised in that:
The density of the nano-titanium dioxide is 3.8~3.9g/cm3。
7. micro-ablation lightweight phenolic resin according to claim 1, it is characterised in that:
The melting temperature of the hollow glass micropearl is 400~600 DEG C.
8. micro-ablation lightweight phenolic resin according to claim 2, it is characterised in that:
The density of the micro-ablation lightweight phenolic resin is less than 1.1g/cm3, Residual carbon at 900 DEG C is greater than 70%.
9. the preparation method of micro-ablation lightweight phenolic resin according to any one of claims 1 to 8, which is characterized in that institute
The method of stating includes the following steps:
(1) by 5~15 parts of hollow phenolic aldehyde microballon, 3~8 parts of nano-titanium dioxide, 5~20 parts of hollow glass micropearl and zirconium diboride
5~15 parts are uniformly mixed, and obtain mixed fillers, then the mixed fillers are divided into etc. to more parts of weight；
(2) 0.3~0.8 part of toughener is added into 100 parts of phenolic resin and stirs evenly, obtains mixture；
(3) the more parts of mixed fillers for obtaining step (1) are sequentially added in the mixture that step (2) obtains and are stirred equal
It is even, micro-ablation lightweight phenolic resin is made.
10. preparation method according to claim 9, it is characterised in that:
In step (2), the phenolic resin is the phenolic resin for carrying out the pre-heat treatment at 60~70 DEG C and crossing；And/or
In step (2), the time of the stirring is 15~20min；And/or
In step (3), when a mixed fillers of every addition are into the mixture, the time of stirring is 10~20min.
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| CN110643143A (en) * | 2019-10-11 | 2020-01-03 | 武汉理工大学 | Resin capable of slight ceramic reaction and preparation method of composite material thereof |
| CN110951209A (en) * | 2019-12-09 | 2020-04-03 | 江苏中昌绝热技术工程有限公司 | High-elasticity ablation-resistant heat-insulating material and preparation method thereof |
| CN111440414A (en) * | 2020-04-16 | 2020-07-24 | 中国一冶集团有限公司 | Novel heat-insulating material and preparation method thereof |
| CN112724439A (en) * | 2020-11-23 | 2021-04-30 | 航天特种材料及工艺技术研究所 | Light heat-insulating micro-ablation prepreg and preparation method thereof |
| CN112920442A (en) * | 2021-01-29 | 2021-06-08 | 中国人民解放军国防科技大学 | Resin-based heat-proof composite material with surface coated with high-temperature infrared stealth coating and preparation method thereof |
| CN113174122A (en) * | 2021-04-20 | 2021-07-27 | 贵州国锐鑫节能科技有限公司 | Organic composite fireproof insulation board and preparation method and application thereof |
| CN115195254A (en) * | 2022-05-30 | 2022-10-18 | 航天特种材料及工艺技术研究所 | Heat insulation/ablation-resistant heat protection structure and preparation method thereof |
| CN115625897A (en) * | 2022-12-12 | 2023-01-20 | 北京玻钢院复合材料有限公司 | Toughening low-density hot-melt phenolic resin prepreg, composite material and preparation method |
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| CN112920442A (en) * | 2021-01-29 | 2021-06-08 | 中国人民解放军国防科技大学 | Resin-based heat-proof composite material with surface coated with high-temperature infrared stealth coating and preparation method thereof |
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| CN113174122A (en) * | 2021-04-20 | 2021-07-27 | 贵州国锐鑫节能科技有限公司 | Organic composite fireproof insulation board and preparation method and application thereof |
| CN115195254A (en) * | 2022-05-30 | 2022-10-18 | 航天特种材料及工艺技术研究所 | Heat insulation/ablation-resistant heat protection structure and preparation method thereof |
| CN115195254B (en) * | 2022-05-30 | 2024-04-02 | 航天特种材料及工艺技术研究所 | Heat insulation/ablation resistance heat protection structure and preparation method thereof |
| CN115625897A (en) * | 2022-12-12 | 2023-01-20 | 北京玻钢院复合材料有限公司 | Toughening low-density hot-melt phenolic resin prepreg, composite material and preparation method |
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Application publication date: 20190719 |
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